Thiocyano-alkyl ethers of the phenylphenols



Patented Jan. 2, 1940 UNITED STATES PATENT OFFICE THIOCYANO-ALKYL ETHERS OF THE PHENYLPHENOLS John E. Livak, Gerald H. Coleman, and Clarence L. Moyle, Midland, Mich, assignors to The Dow Chemical Company, Midland,

tion of Michigan Mich, a corpora- No Drawing. Application October 27, 1938,

' Serial No. 237,276

10 Claims.

wherein n represents an integer from 2 to 5, inclusive, and X represents a member of the group consisting of lower alkyl, chlorine, bromine, and hydrogen. These compounds are for the most part low-melting solids or viscous, high-boiling, water-white liquids, substantially insoluble in water and somewhat soluble in most petroleum distillate fractions and organic solvents generally. We have prepared representative members of this group of compounds and found that they are useful as insecticidal toxicants, particularly when dissolved in petroleum distillate fractions.

Our new compounds may be prepared byreacting a halo-alkyl ether of a phenylphenol or a nuclear substituted derivative thereof with an alkali metal thiocyanate in the presence of alcohol. For example, a suitable halo-alkyl ether and the inorganic thiocyanate are dispersed in absolute alcohol and the resulting mixture heated to its boiling temperature and under reflux for a period of time suflicient to accomplish .reaction. The reaction temperature is generally between about and C., although somewhat lower or higher temperatures may be employed, the reaction being carried out under autogenous pressure where temperatures above the boiling point of the solution prevail. While any suitable proportions of the halo-alkyl ethers of the phenylphenol and the metal thiocyanate may be employed, substantially equi-molecular proportions thereof have been found to give the desired compounds in good yield. Following the reaction, the mixture is treated to isolate the thiocyano-alkyl ether of the phenol. This may be accomplished, for example, by fractionally distilling the reaction mixture to remove the major portion of the alcohol, diluting the residue with water, and extracting with benzene or ethylene chloride to recover the water-immiscible organic thiocyanate. The extracting solvent is then distilled out of the mixture to leave a crude'ether product which may be employed as such for insecticidal purposes or, if desired, further purifled as by fractional distillation.

The halo-alkyl ethers employed as reactants in the preparation of our new compounds may be prepared by reacting an alkali metal salt of a phenylphenol with an equ-imolecular proportion of an alkylene halide or poly-methylene halide under such conditions ,of temperature and pressure as favor the replacement of a single halogen atom by the phenyl-phenoxy group. The halo-alkyl ether of the phenylphenol is there-' after separated from the reaction mixture as by fractional distillation. Co-pending applications Serial Nos. 90,380, filed July 13, 1936 and 139,581, filed April 28, 1937, by Coleman et a1.

describe the preparation and properties of a construed as limiting the same:

Emampe 1 99 grams (0.4 mol) of gamma-chloro-propyl ether of Z-phenylphenol (boiling point 147 to 149 C. at 3 millimeters pressure), 30 grams (0.4 mol) of potassium thiocyanate, and 300 milliliters of absolute alcohol were mixed together and heated at 79-81 C. and under reflux for 48 hours. The mixture was then fractionally distilled to remove a major proportion 'of the alcohol, and the distillation residue poured into an excess of water with stirring, whereby a water-immiscible oil wasseparated. This oil was taken up by extraction of the benzene, and the extract dried and fractionally distilled, whereby there was obtained 50 grams (0.2 mol) of gammathiocyano-propyl ether of Z-phenylphenol as a water-white liquid boiling at 198 to 200 C. at 2 millimeters pressure and having a specific-gravity of 1.158 at 20/4 C. A 3 per cent solution of this compound in kerosene, when tested by the' Feet-Grady method, substantially as described in Soap, 8, No. 4, 1932, gave a knockdown of per cent in 10 minutes and a kill or 88 per cent in 48 hours against three-day'old house flies.

Example 2 In a similar manner, equimolecular proportions of beta-bromo-ethyl ether of B-phenylphenol (boiling point -192 C. at 4 millimeters pressure) and potassium thiocyanate were reacted together in alcohol dispersion, wherebygthere was obtained 68.6 per .cent yield of the beta-thiocyano-ethyl ether of 3-phenylphenol as a viscous liquid boiling at 207-212 C. at 2 millimeters pressure. A 3 per cent solution of this compound in kerosene, when tested by the Peel:- Grady method, gave a knockdown of 100 per cent in 1.0 minutes and a kill of 76 per cent in 48 hours against three-day old house flies.

Example 3 100 grams (0.32 mol) of beta-bromo-ethyl ether of Z-phenyl--chloro-phenol (boiling at 184 to 187 C. at 6.3 millimeters pressure), 81 grams (0.32 mol) of potassium thiocyanataand 125 milliliters of absolute alcohol were mixed together and refluxed with stirring for 11 hours.

Example 4 71.0 grams (0.21 mol) of the beta-bromo-ethyl ether of 2-phenyl- 4-tertiarybuty1 phenol (boiling at 210-215 C. at 8.6 millimeters pressure), 20.7

. grams (0.214 mol) of potassium thiocyanate, and

100 milliliters of absolute alcohol were reacted together substantially as described in Example 3. Fractional distillation of the crude reaction mixture yielded 25.4 grams of the beta-thiocyanoethyl ether of 2-phenyll-tertiaryhutyl phenol as a viscous oil boiling at 225 to 230 C. at 5.3 millimeters pressure and having a specific gravity of In a similar manner, other halo-alkyl ethers of the 'phenylphenols were reacted with the alkali metal thiocyanates to obtain representative organic thiocyanates as follows:

Beta-thiocyano-ethyl ether of 2-phenylpl1enol, by the reaction of potassium thiocyanate with the beta-bromo-ethyl ether of 2-phenylphenol (melting point 67 C;). This compound is a colorless oil boiling at 182 to 186 C. at 3 millimeters pressure and having a specific gravity of 1.191 at 20/4 C. A 3 per cent solution of the beta-thioc'yano-ethyl ether of 2-phenylphenol in kerosene, when tested by the Feet-Grady method, gave a knockdown in 10 minutes of 89 per cent and a kill in 48 hours of 68 per cent against threeday old house flies.

Gamma-thiocyaho-propyl ether of 3-phenylphenol, by the reaction of gamma-bromo-propyl ether of S-phenylphen'ol (boiling point 200 to 205 C. at 4 millimeters pressure) withpotassium thiocyanate. This thiocyano-alkyl ether is a colorless oil boiling at 2 l3to 246 C. at 5 millimeters pressure. A 3 per cent solution of this compound in kerosene, when tested as described in the foregoing examples, gave a knockdown in 10 minutes of 92 per cent and a kill in 48 hours of 74 per cent.

Beta-thiocyano-ethyl ether of -phenylphenol, by the reaction of beta-bromo-ethyl ether of 4- phenylphenol (melting point 114 C.) with potassium thiocyanate. This organic thiocyanate is a white, crystalline solid melting at 100 to 102 C.

Other halo-alkyl ethers of the phenylphenols which may be reacted with the alkali metal thiocyanates, substantially as described in the foregoing examples to produce valuable compounds, are beta-chloro-ethyl ether of Z-phenylphenol, boiling at 174 to 176 C. at 10 millimeters pressure; beta-chloro-ethyl ether of S-chlorophenylphenol. boiling at 179 to 181 C. at 5 millimeters pressure; beta-chloro-ethyl ether of 4- phenylphenol, boiling at 163 to 165 C. at 3 millimeters pressure; gamma-chloro-isobutylether of 2-phenylphenol boiling at 1 70 to 173 C. at 5 millimeters pressure; beta-chloro-ethyl ether of 2-phenyl-4-chloro-phenol, boiling at 149 to 150 C. at 3 millimeters pressure; beta-chloro-ethyl ether of 2-phenyl-4-isopropyl phenol, boiling at 150 to 153 C. at 2 millimeters pressure; betachloro-ethyl ether of Z-hromol-phenylphenol; beta-bromo-ethyl ether of 2-methyl-4-phenylphenol; beta-chloro-propyl ether of 2-phenylphenol; chloro-pentyl ether of B-phenylphenol;

and the like.

-We claim:

1. A compound having the formula oo..Hz.soN

wherein n represents an integer from 2 to 5, in-

clusive, and X represents a member of the group consisting of chlorine, bromine, lower alkyl, and

' hydrogen.

2. A compound having the formula ooflm..soN wherein n represents an integer from 2 to 5, in-

clusive.

3. A compound having the formula Gil wherein X rep-resents a member of the group consisting of chlorine, bromine, lower alkyl, and

hydrogen.

4. A compound having the formula OC2H4SCN 5. A compound having the formula ;2CC3H6SCN 6. A compound having the formula OC,.H2,.SCN

wherein n is an integer between 2 and 5, in-

clusive.

7. A compound having the formula JOHN E. LIVAK. GERALD H. COLEMAN. CLARENCE L. MOYLE. 

